Sulfur-containing derivatives of methylolated aminotriazines



United States Patent 3,530,086 SULFUR-CONTAINING DERIVATIVES 0F METHYLOLATED AMINOTRIAZINES Daniel Porret and Ewald Forster, Binningen, and Juerg Maurer, Riehen, Switzerland, assignors to Ciba Limited,

Basel, Switzerland, a company of Switzerland No Drawing. Filed Feb. 13, 1968, Ser. No. 705,012 Claims priority, application Switzerland, Feb. 24, 1967, 2,737 67 Int. Cl. C08g 9/04; C07d 55/20, 55/22 US. Cl. 260-301 3 Claims ABSTRACT OF THE DISCLOSURE It is known to increase substantially the curing speed of aminoplast moulding compositions, especially melamine resin moulding compositions, by the addition of catalysts e.g. acids, acid anhydrides, acid amides or salts of organic bases, and thereby to produce industrially valuable, quickcuring moulding compositions. Such moulding compositions have, however, the serious disadvantage that their fiowability and storability are impaired.

It is further known that by the addition of plasticizers e.g. p-toluenesulphonamide derivatives, monocresyl glyceryl ethers or 2-ethyl-l,3-hexanediol, the flowability and the fissuring stability of aminoplast moulding compositions, especially melamine resin moulding compositions, can be improved. However, the use of such plasticizers in general impairs essential technical properties of the mouldings made from aminoplasts. Thus, for example, plasticizers that contain hydroxyl groups or other polar plasticizers may considerably increase the water absorption and thereby adversely affect the electrical properties of the finished articles. Moreover, most plasticizers affect the mechanical properties and the heat stability of the finished articles unfavourably.

The present invention provides a new type of plasticizers, namely trans-etherification products of about 2 mols of a methylolated 1,3,5-aminotriazine, containing at least 2 amino groups, highly etherified with a lower alcohol, and 1 mol of a dihydric aliphatic alcohol containing at least one thioether bridge; these compounds are surprisingly eminently suitable for use as plasticizers in the manufacture of quick-curing and nonetheless well flowing, storable aminoplast moulding compositions, especially melamine resin moulding compositions. Particularly suitable among them is a trans-etherification product of about 2 mols of hexamethylolmelamine pentamethyl or hexamethyl ether with thiodiethyleneglycol. An addition of a small quantity below 10% by weight, advantageously by weight, of this substance, referred to the weight of the moulding composition as a whole, apart from the conventionally used curing catalysts, sufiices as a rule to produce all the afore-mentioned advantages of the aminoplast moulding composition, especially melamine resin moulding composition.

Accordingly, the present invention is concerned with new plasticizing additives for quick-curing aminoplast moulding compositions, being sulphur-containing derivatives of iii ice

methylolated aminotriazines, such as are obtained when (I) 1.8 to 2.2 mols, preferably about 2 mols, of a methylolated amino-s-triazone containing at least two amino groups, more than of Whose methylol groups are etherified with a lower aliphatic alcohol containing 1 to 4 carbon atoms, is condensed with (II) 1 mol of an aliphatic dialcohol or dimercaptan containing at least one thioether bridge at an elevated temperature.

From the highly etherified methylolated amino-s-triazines, used as starting materials for the manufacture of the new aminotriazine derivatives of this invention, there are particularly suitable condensation products of melaine, highly etherified with a C to 0., alcohol such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol or tertiary butanol, with formaldehyde.

Such condensation products may contain 1 to 6 methylol groups and are as a rule mixtures of difierenet compounds. There may be mentioned trimethylolmelamine highly etherifield with a C to C alcohol and especially hexamethylolmelamine, more especially .hexamethylolmelamine pentamethyl and hexamethyl ether. Further suitable are methylol compounds, highly etherified with C to C alcohols, of guanamines such as formoguanamine, acetoguanamine, n-butyroguanamine,. isobutyroguanamine, methacryloguanamine, sorboguanamine, n-valeroguanamine, caproguanamine, heptanoguanamine, capryloguanamine, 4-ethyl-2-octanoguanamine, .stearoguanamine, linoleoguanamine, A -tetrahydrobenzoguanamine, hexahydrobenzoguanamine, 3-methyl-A -tetrahydrobenzoguanamine, 3 methylhexahydrobenzoguanamine, 3,4-dimethyl-A -L2, 5,6 tetrahydrobenzoguanamine, 3,-4 dimethylhexahydro benzoguanamine; phenylacetoguanamine, tolylacetoguanamine, benzoguanamine, ortho-, metaand para-toluguanamine, ortho-, metaand para-xyloguanamine, uand fl-naphthoguanamine; furthermore of diguanamines e.g. those of the formula (which y is a small digit) such as adipoguanamine. There may be mentioned the tetramethylolbenzoguanamine and tetramethylolacetoguanamine highly etherified with a C to C alcohol.

Further suitable are formaldehyde condensation products, highly etherified with a C to C alcohol, of N-substituted melamines such as N-butylmelamine, N-phenyl- -melamine, N-tolylmelamine, N-cyclohexylmelamine, N,N-

diallylmelamine, N,N-dibenzylmelamine, N-tertiary octylmelamine. Further suitable are methylol compounds, highly etherified with C to C alcohols, of those derivatives of melamine which still contain at least two amino groups eg methylol compounds of melam, melem, ammeline or ammelide, of halogenated aminotriazines such as 2-chloro-4,6-diamino-1,3,5-triazines, or of aminotriazines substituted by alloxy groups, such as 2-alloxy-4,6- diamino-l,3,5-triazine.

As aliphatic dihydric alcohols or dimercaptans containing at least one thioether bridge, which according to this invention are condensed with the highly etherified, methylolated amino-s-triazines, there are particularly suitable compounds of the general formula r 1 11 X-R1 -l -XR2S-R3-X R -X----- l L 4 J H in which X represents an oxygen or a sulphur atom, R to R are identical or difierent linear or branched alkylene residues, and m and 11 each is a whole number from 1 to 4.

A preferred compound of the formula (II) is the thiodiethyleneglycol of the formula HOC H SC H OH which is readily accessible by condensing 1 mol of H 8 Suitable urea derivatives are e.g. alkylureas and thioureas, arylureas and thioureas, alkyleneureas and diureas such as ethylene or propylene urea, dihydroxyethylene urea and acetylene diurea.

As aminotriazine components of the said condensation With 2 H1015 of ethylene OXide- It is also P055331e to 1186 5 products there are suitable, apart from melamine, above the thiodipfopyleneglycol Obtained y Condensing 2 mols all also N-substituted melamines such as N-butylmel of p py OXide With 1 H101 of 2 adducts of amine, N-phenylmelamine, N-tolylmelamine, N,N-diallyl- 1 to 16 mols of ethylene oxide or propylene oxide With melamine and N-tertiary octylmelamine, as well as mel- 1 mol of thiodiethyleneglycol or thiodipropyleneglycol. am, melem, ammeline, ammelide, 2,4-diamino-6-phenyl- A particularly good plasticizer for quick-curing melamino-1,3,5-triazine; aminotriazines substituted by allylamine resin moulding compositions is the condensation oxy groups; guanamines such as formoguanamine, acetoproduct of approximately 2 mols of hexamethylol melguanamine, caproguanamine, capryloguanamine, lauroamine hexamethyl ether or pentamethyl ether and 1 mol guanamine, stearoguanamine, linoleoguanamine, A -tetra 0f thiodielhyleneglycol 0f the formula hydrobenzoguanamine, hexahydrobenzoguanamine, ben- CH2OCH2 N CH2-OCH3 N-G CN OH;-OC1'-I N CH2OCH3 l H CHr-O-CHz N N OI-I2OCH2CH2SOH2CHzOCHz-NO CN The condensation and trans-etherification respectively of the highly etherified amino-s-triazine+formaldehyde condensate is performed by known methods e.g. advantageously by heating the starting materials in the presence of an acid catalyst e.g. phthalic anhydride, in an inert gas and under reduced pressure, during which the lower alcohol released by the trans-etherification distils over.

In general, the reaction products are colourless liquids or syrups of medium to high viscosity.

As mentioned above, the new sulphur-containing amino-triazine derivatives are used as plasticizing additives for quick-curing aminoplast moulding compositions.

Accordingly, the present invention includes also aminoplast moulding compositions containing a curable aminoplast, preferably a curable melamine resin, a curing catalyst and a plasticizer, characterized in that the plasticizer consists of a condensation product of (I) 1.8 to 2.2 mols, preferably 2 mols, of a methylolated amino-s-triazine containing at least two amino groups, more than 80% of whose methylol groups are etherified with a lower aliphatic alcohol containing 1 to 4 carbon atoms, and (II) 1 mol of a dialcohol or dimercaptan containing at least one thioether bridge.

As a rule, the said plasticizer is used in an amount of less than 10% and preferably of about 5% by weight, referred to the weight of the aminoplast moulding composition as a whole.

The term curable aminoplast as used in this context has the meaning generally used in the trade. In the first place it describes the known, still soluble and fusible, condensation products of formaldehyde with urea or above all with melamine. As is known, such condensation products can be converted by heating, in most cases in the presence of a suitable curing catalyst and, if necessary, with application of pressure, into synthetic products having valuable technical properties; they are of special industrial value in the lacquer, laminate and moulding composition sectors. The term curable aminoplast further includes quite generally the still soluble and fusible condensation products of aldehydes, especially formaldehyde, if desired in combination with other aldehydes, such as acetaldehyde, butyraldehyde, benzaldehyde, salicylaldehyde, glyoxal, acrolein, furfural and crotonaldehyde, with so-called aminoplast formers such as urea, thiourea, cyanamide, dicyandiamide, aminotriazines, urethanes, guanidine, amino rhodamide, metal rhodamides such as calcium or aluminum rhodamide, guanylthioureas and other urea derivatives and their methylol compounds.

zoguanamine, orth0-, metaand para-toluguanamine and diguanamines e.g. those of the general formula in which y is a small number, such as adipoguanamine.

Hydroxylated residues in the condensation products, such as methylol groups, may be wholly or only partly etherified with methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, methylcyclohexanol, borneol, isoborneol and/or other saturated alcohols. The etherification may also be performed with unsaturated alcohols such as allyl alcohol, methallyl alcohol or 2-buten-1-ol, abietinol and partially etherified dihydric or polyhydric alcohols, inter alia with alkoxyethanols, alkoxypropanols. Condensates containing free hydroxyl groups may also have been etherified by reaction with an alkylene oxide, such as ethyelne oxide, 1,2-propylene oxide, 1,2-butylene oxide or the like, the adducts being stabilized by blocking the terminal groups. Suitable urethanes are above all lower alkylurethanes such as methylurethane, ethylurethane or butylurethane and their methylol derivatives, e.g. methylolbutylurethane. The curable aminoplast resins, which may be incorporated with the moulding compositions of this invention, may also contain modifying additives or they may have been sulphated; such additives are phenol, cresols, xylenols, butylphenols, octylphenols and nonylphenols, and also salicylic acid, especially in the form of pro-condensates based on formaldehyde+phenol, +cresol or +xylenol, and these methylol compounds or more highly condensed novolaks may be added at any desired condensation stage. Further suitable additives are proteins such as acid casein, alkyd resins, aniline and alkylanilines and their formaldehyde resins; carboxylic acid amides such as acetamide, hexamethylenetetramine, ethylenimino polymers such as natural resins e.g. colophony or copal resin. Sulphation is generally carried out by adding sulphur or a sulphur donor, such as hydrogen sulphide, pyrosulphuric acid dichloride, ammonium sulphide or a polysulphide.

Among known catalysts, which can be used in the present moulding compositions, there are particularly suitable organic acids and their anhydrides e.g. isophthalic acid, phthalic anhydride, terephthalic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, men chamber (diameter 30 mm.) into a thermostat-condihydrocinnamic acid, benzoic acid, toluenecarboxylic trolled flow channel of constant cross-section (10 x 4 mm.) acid, trimesic acid, citric acid, tartaric acid and pyromelagainst a counterweight (4 kg). The path of the counterlitic dianhydride. Furthermore, there may be mentioned weight (=flow path) is plotted on a graph as a funcso-called latent curing catalysts such as the methyl and tion of the flow time. ethyl esters of n-toluenesulphonic acid which, under the 0 The moulding compositions mentioned in the example pressure and temperature conditions used in pressing, were tested as tablets under the following conditions, give ofi free acid e.g. p-toluenesulpohnic acid. As such without any pretreatment. latent curing agents there may also be used inorganic Test gear: ZWICK & Co., Einsingen bei Ulm, Type Z 460. metal salts e.g. zinc sulphate. 10 Test temperature: 160 C.

The moulding compositions may contain further con- Specific pressure on tablet: 120 kg./cm. ventional additives, especially fillers and/or reinforcing (3) Tendency to cracking agents e.g. glass fibres, asbestos fibres, mlca, kaolin, ground dolomite, quartz meal, wood meal and especially cellulose, In P Internal expel'lment the tendency to cracklng of also mould release agents e.g. stearic acid or zinc stearate. mouldmgs P P manufactured y the Compared with the known aminoplast moulding comcalled transfel' l pf mouldlng P under the positions the new aminoplast moulding compositions of under-mefltloned Colldltlons, Was tested! q} Y this invention, especially those based on curable melamine P F- Press temperature 'Curlng t1II 1e 5 i fif r h follo ing advantages; minutes. The tendency to cracking Was evaluated in a short-time test after thermal ageing for 24 hours at 120 Higher curing speed without substantial impairment of the in a drying cabinet.

flowability and storability of the aminoplast moulding compositions. 7 EXAMPLE 1 Diminished tendency of the moulding to crack and to turn A mixture of 975 of a liquid methylolmelamine yellowlsh at elevated temperature' methyl ether (containing per molecule 5.2 methylol ether The fastness to light of the mouldings is not reduced. This 25 groups and 0.2 free methylol group) 160 g of thiodi enables the costly a nd less light-fast melam1ne+phenol ethyleneglycol and 007 g of phthalic anhydride was moulding COIHPOSIUOIIS to be replaced by substantially heated under nitrogen to 0 in a flask equipped with Cheaper, llght-fast productsagitator and boiling capillary. Under a vacuum of about Unless otherwise indicated, parts and percentages in 250 Within 2 hours, 81 y- 80 of the following examples are by weight. The flowability and methanol are distilled off. Shortly before termination of tendency to cracking of the mouldings described in the t reaction the Va uum iS gradually improved to 18 mm. following specific examples were tested by the following 1050 grams of a colourless resin are ta d WhiCh methods: has a viscosity of about 57,000 cezntipoises at 25 C.

(1) Measuring the cup value EXAMPLE 2 In this testing method (developed by ourselves) 70 g. of the moulding composition are introduced into a cup mlxtul'e of 780 gof crystalllne hfixamethylolmela' mould according to DIN 53,465, heated at 150 0., and mm hexamethylvether, 1 a of thiodiethyleneglycol and a test moulding is made. On the test moulding the followof phthallc anhydride is heated under nitrogen to ing values are measured; 40 145 in a flask equipped With an agitator and a boiling capillary. Under a vacuum of about 300 mm. Hg, 61 g. of methanol are distilled 010? within 4 hours. The last remnants of methanol are distilled off under a vacuum of 18 mm. Hg.

797 grams of a colourless resin are obtained which A fully moulded cup without flash fin is given the cup has a viscosity of about 5000 centipoises. It consists valve 7. When the flowability under the moulding presmainly of the compound of the formula CH3OCH2 N CH2OCH3 N-O C CH2OCH2 N CHa-O-CHa l l t\ y CHa-O-CH2 N\ CH2OCHz-CH2S-CHzCH2OCH2-N-C (a) mean height of the test moulding, if it has no flash fin;

(b) if the test moulding has a flash fin, the weight of this fill.

CHz-O-CHs CH2OCH3 sure used is insufficient to fill the mould entirely, the EXAMPLE 3 mean height of the moulding obtained is measured with a scale of equal divisions, which starts with 0 at the bottom of the cup and whose scale division 7 coincides with the top edge of the fully moulded cup.

In the case of test mouldings having a flash fin the evaluation is carried out as follows: The flash fin is removed and weighed and the cup value calculated from the A melamineJ-t-formaldehyde resin solution (molecular ratio of melaminezformaldehyde=l:3) was prepared by condensing melamine and formaldehyde at 80 C. in an aqueous alkaline medium, and the condensation product of methylolmelamine methyl ether and thiodiethyleneglycol, described in Example 1, was added as plasticizer,

65 and this mixture was used for impregnating cellulose. The

formula resulting product was then dried, comminuted and ground p Weighc of fiash fin in g. for 15 hours in a ball mill with phthalic anhydride and 2 zinc stearate. The resulting moulding composition A had the following composition:

The upper limit of the scale is the cup value 10, corresponding to a weight of the flash fin of 6 g. or more. Me1amin+fmma1dehyde resin Parts by g; (2) Determining the flowability with the flowmeter accord- Cellulose 33 ing to von Meysenburg/ZWICK Zinc stearate 0.95

According to DIN 53,478 the moulding composition is Phthalic anhydride 0.05

expressed in this test from a thermostat-controlled speci- Plasticizer of Example 1 5 Then a known moulding composition B was prepared exactly as the moulding composition A of this invention, with the only difierence that no parts of plasticizer of Example 1 were added.

Standardized mouldings were then made from the two moulding compositions A and B. The properties of the moulding compositions and mouldings are compared in the following table. In all experiments the moulding conditions were identical, namely:

Prewarming the moulding composition for minutes at 105 C. in a drying cabinet; moulding at 160 C. under a pressure of 35 tons on the press. Moulding time for VSM bars was 3 /2 minutes and for DIN bars 5 /2 minutes.

What is claimed is:

1. A moulding composition containing (1) a curable aminoaldehyde resin (2), a curing catalyst and (3) as plasticizer the heat-condensation product of (I) 1.8 to 2.2 mols of a methylolated amino-s-triazine containing at least two amino groups, and more than 80% of whose methylol groups are etherified with a lower aliphatic alcohol containing 1 to 4 carbon atoms, with (II) 1 mol of a member selected from the group consisting of a dialcohol containing at least one thioether bridge and a dimercaptan containing at least one thioether bridge.

2. A moulding composition according to claim 1, wherein the plasticizer (3) is used in an amount of less than 10%, by weight, referred to the total weight of the moulding composition.

3. A moulding composition according to claim 1, wherein the plasticizer 3) is the compound of the formula 0113-0-0112 N CI-Ir-O-OH;

\ /N(|J (|3N\ CH3-OCH2 N\ CH2OOH3 CHaOCH2 N /N OH2OCH2-OH2S-OH2CHzOCHz-N? (HJN\ (|J/OHz-OCH; N CHzO-OH N\ ([J/OH -O-CH CI-I OOH N\ CHr-OCH Moul iing M 1d References Cited com os1 1011 on in A wit compositior l UNITED STATES PATENTS plasticizer B without Properties of the moulding composition of Example 1 plasticizer 3,141,885 7/ 1964 ROSS $11 a1 260249.6 Flowability on the cup at 500 kp./cm. 3,267,099 8/1966 Acker 260249-8 F1160 h2lue) f "M. 9.5 7 R18 B ow elg on es gear 0 von eysen- 1(ourg/ZWIGK at 120 kp./cm. 160 0. 160 30 3 MOR LIE Primary Examiner mm. D i Minimum press time to produce blistep W. H. FLETCHER, Assistant Examlner P free p l ates a t lw" C s econds) 25 roper eso emou mg: ilmpagtisttregigthvshtl crnkpjcnfly. 5. 69 5.23 U S Cl X R eat s or ion poin aecor ing ISO/R 193 191 260 249.6, 249.8, 249.9 Dielectric constant E, 60 c./sec., 25 C. 8.0 8. 1 40 Ohmic resistance (ohmXcm.) 1. 0x10 2. 3X10 Arc resistance VDE 0303 (stage) L4 L4 Absorption of cold water, 20 C within 24 hours, percent 0.2 0. 2 Tendency to cracking after ageing for 24 hours at C Light-fastness after 400 hours, ana1ogous to DIN 54004 (Xeno test) 5 l Slight. 2 Very strong. 3 Very good.. 

